JP4720562B2 - Coextruded multilayer film and packaging material using the film - Google Patents
Coextruded multilayer film and packaging material using the film Download PDFInfo
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- JP4720562B2 JP4720562B2 JP2006074154A JP2006074154A JP4720562B2 JP 4720562 B2 JP4720562 B2 JP 4720562B2 JP 2006074154 A JP2006074154 A JP 2006074154A JP 2006074154 A JP2006074154 A JP 2006074154A JP 4720562 B2 JP4720562 B2 JP 4720562B2
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- 239000005022 packaging material Substances 0.000 title description 17
- 239000011347 resin Substances 0.000 claims description 142
- 229920005989 resin Polymers 0.000 claims description 142
- 229920001684 low density polyethylene Polymers 0.000 claims description 53
- 239000004702 low-density polyethylene Substances 0.000 claims description 53
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 39
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 38
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 21
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 17
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 229920005672 polyolefin resin Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 108
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- -1 cyclic olefin Chemical class 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
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- 238000004806 packaging method and process Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 11
- 229920001748 polybutylene Polymers 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 8
- 239000005001 laminate film Substances 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 6
- 238000009820 dry lamination Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
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- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KWDGBSOXFVYDLF-UHFFFAOYSA-N C12C(C3C(C=4C5=CC=CC=C5CC1=4)C3)C2 Chemical compound C12C(C3C(C=4C5=CC=CC=C5CC1=4)C3)C2 KWDGBSOXFVYDLF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- RNWDNEVYZAPIBG-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OC)C2 RNWDNEVYZAPIBG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、食品、薬品、医療器具、工業部品、雑貨、雑誌等を包装する包装材に関するものであって、詳しくは手による引き裂き性がフィルムの縦方向のみならず横方向でも良好であり、かつ容易に手で開封可能なヒートシール強度を有する共押出多層フィルム及び該フィルムからなる包装材に関する。 The present invention relates to a packaging material for packaging foods, medicines, medical instruments, industrial parts, miscellaneous goods, magazines, etc., and in particular, tearability by hand is good not only in the vertical direction of the film but also in the horizontal direction, The present invention also relates to a coextruded multilayer film having heat seal strength that can be easily opened by hand, and a packaging material comprising the film.
従来、包装材には内容物の保護の観点から、高ヒートシール強度、耐ピンホール性が要求される。一方、近年のユニバーサルデザイン重視傾向の中で、社会的弱者（高齢者、幼児、障害者等）への配慮として、簡単に手で開けられる易開封性が要求されている。易開封性とは、はさみ、ナイフ等の開封治具を用いることなく手で簡単に開封できる性能をいう。易開封性を付与する方法としては、（１）フィルムの縦方向や横方向に引き裂きやすくする（以下、「易カット性」という。）方法、（２）包装材のヒートシール部が適度なヒートシール強度となるようにしてヒートシール部を引き剥がしやすくする（以下、「イージーピール性」という。）方法があるが、従来は、易カット性又はイージーピール性のいずれか一方の性能を付与することにより、易開封性を実現していた。 Conventionally, a packaging material is required to have high heat seal strength and pinhole resistance from the viewpoint of protecting contents. On the other hand, in the recent trend of emphasizing universal design, easy-openability that can be easily opened by hand is required as a consideration for the socially vulnerable (elderly, infants, disabled, etc.). Easy-openability means the ability to be easily opened by hand without using an opening jig such as scissors or a knife. As a method for imparting easy-openability, (1) a method of making the film easy to tear in the longitudinal direction or the lateral direction (hereinafter referred to as “easy-cut property”), and (2) a heat seal portion of the packaging material having an appropriate heat. Although there is a method of making the heat seal part easy to peel off so as to have a sealing strength (hereinafter referred to as “easy peel property”), conventionally, it provides either easy-cut property or easy peel property. As a result, easy opening was realized.
しかし、易カット性を有する包装材においては、引き裂きを容易にする切れ目（ノッチ）がない場合、あるいは切れ目が不十分である場合、容易に開封できないことがあった。一方、イージーピール性を有する包装材においては、持ち手のタブ部（開封口）が小さすぎる場合、あるいは殺菌時や物流輸送工程での破袋等を防止するため、ヒートシール強度を高くした場合、消費者が実際使用する際に容易に開封できないことがあった。また、医療現場で用いられている医療器具等の包装材は、短時間に確実に開封できないと、生命にかかわる緊急事態も発生し、大きな問題となる。したがって、開封治具等が手元になくても手で容易に開封でき、その開封方法も２つ以上あって、一方の開封方法で容易に開封できなくても、他方の開封方法で容易に開封できることが求められている。そこで、近年においては、どのような状況下でもより確実に開封できるよう易カット性及びイージーピール性の両方の性能を有する包装材が必要となってきている。 However, in the case of a packaging material having easy-cutting properties, there are cases where opening is not easy when there is no cut (notch) that facilitates tearing or when the cut is insufficient. On the other hand, in the case of packaging materials with easy peel properties, when the tab portion (opening opening) of the handle is too small, or when the heat seal strength is increased to prevent bag breakage during sterilization or logistics transportation When the consumer actually uses it, it may not be opened easily. In addition, packaging materials such as medical instruments used in the medical field cannot be reliably opened in a short time, which may cause a life-threatening emergency and become a serious problem. Therefore, even if there is no opening jig etc., it can be easily opened by hand, and there are two or more opening methods, and even if it cannot be opened easily by one opening method, it can be easily opened by the other opening method. There is a need to be able to do it. Therefore, in recent years, a packaging material having both easy-cutting properties and easy peel properties has become necessary so that it can be opened more reliably under any circumstances.
上記の問題を解決するものとして、環状オレフィン系樹脂を主成分とした環状オレフィン系樹脂組成物から形成された第１の層と、オレフィン系（共）重合体またはそれを含む組成物から形成された第２の層との少なくとも２層が積層されてなるポリオレフィン系多層積層体が提案されている（例えば、特許文献１参照。）。このポリオレフィン系多層積層体は、環状オレフィン系樹脂組成物から形成された第１の層の厚さが該多層積層体の厚さの７０％（７０μｍ）と厚い上、第２の層には剛性の高いポリプロピレン系樹脂を使用しているため、柔軟性に乏しく、屈曲に対する耐ピンホール性に問題があった。さらに、このように剛性が高い樹脂を使用しているため、多層積層体の厚さが１００μｍ以上ある場合、手で引き裂くことは子供や高年齢者層の人にとって困難で、十分な易カット性が得られない問題があった。また、層間密着性（ヒートシール強度）を高めることはしているが、イージーピール性は考慮されておらず、易開封性が十分ではなかった。 In order to solve the above problems, the first layer formed from a cyclic olefin resin composition mainly composed of a cyclic olefin resin and an olefin (co) polymer or a composition containing the first layer is formed. Further, a polyolefin-based multilayer laminate in which at least two layers with the second layer are laminated has been proposed (for example, see Patent Document 1). In this polyolefin-based multilayer laminate, the thickness of the first layer formed from the cyclic olefin-based resin composition is as thick as 70% (70 μm) of the thickness of the multilayer laminate, and the second layer is rigid. Since a high-polypropylene resin is used, the flexibility is poor and the pinhole resistance to bending is problematic. Furthermore, since such a highly rigid resin is used, when the thickness of the multilayer laminate is 100 μm or more, tearing by hand is difficult for children and elderly people, and it is easy to cut. There was a problem that could not be obtained. Moreover, although the interlayer adhesion (heat seal strength) is increased, the easy peel property is not considered, and the easy-openability is not sufficient.
また、脂環式構造含有重合体からなる層と、その他の熱可塑性樹脂からなる層とを積層した包装フィルムが提案されている。（例えば、特許文献２参照。）。この包装フィルムは、２０〜４０μｍと薄いため比較的易カット性は良好である。しかし、この包装フィルムにおいても、層間密着性を高めることはしているが、イージーピール性は考慮されておらず、易開封性は十分でなかった。また、上記のポリオレフィン系多層積層体と同様に剛性の高いポリプロピレンや高密度ポリエチレンを外層に使用しているため、柔軟性に乏しく、耐ピンホール性に問題があった。
本発明の課題は、フィルムの縦方向及び横方向ともに容易に引き裂くことができる易カット性と、ヒートシール部を容易に引き剥がすことができるイージーピール性との２種の易開封性を有し、二次成形可能で、かつ屈曲による耐ピンホール性にも耐えられる共押出多層フィルム及び該フィルムを用いた包装材を提供することである。 The object of the present invention is to have two types of easy-opening properties: easy cutability that allows easy tearing in both the vertical and horizontal directions of the film, and easy peelability that allows the heat-sealed portion to be easily peeled off. Another object of the present invention is to provide a coextruded multilayer film that can be secondarily molded and can withstand pinhole resistance caused by bending, and a packaging material using the film.
本発明者らは、鋭意研究した結果、低密度ポリエチレン及び／又は直鎖状低密度ポリエチレンを用いた樹脂層（Ａ）と、低密度ポリエチレン及び／又は直鎖状低密度ポリエチレンと環状オレフィン系樹脂とを用いた樹脂層（Ｂ）と、低密度ポリエチレン及び／又は直鎖状低密度ポリエチレンとブテン−１系重合体とを用いた樹脂層（Ｃ）とを、（Ａ）／（Ｂ）／（Ｃ）の順、又は（Ａ）／（Ｂ）／（Ａ）／（Ｃ）の順に共押出積層法により成膜した３層又は４層の多層フィルムは、易カット性とイージーピール性に優れ、二次成形可能で、かつ屈曲による耐ピンホール性にも優れることを見いだし、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that a resin layer (A) using low-density polyethylene and / or linear low-density polyethylene, low-density polyethylene and / or linear low-density polyethylene, and cyclic olefin resin And a resin layer (C) using low-density polyethylene and / or linear low-density polyethylene and a butene-1 polymer, (A) / (B) / The three-layer or four-layer multilayer film formed by the coextrusion lamination method in the order of (C) or in the order of (A) / (B) / (A) / (C) is easy to cut and easy peel. It has been found that it is excellent, can be secondarily molded, and has excellent pinhole resistance due to bending, and the present invention has been completed.
すなわち、本発明は、低密度ポリエチレン（ａ１）及び／又は直鎖状低密度ポリエチレン樹脂（ａ２）からなる樹脂層（Ａ）と、低密度ポリエチレン（ｂ１）及び／又は直鎖状低密度ポリエチレン樹脂（ｂ２）７０〜９０質量％、及び環状オレフィン系樹脂（ｂ３）１０〜３０質量％を含有する樹脂層（Ｂ）と、低密度ポリエチレン樹脂（ｃ１）及び／又は直鎖状低密度ポリエチレン樹脂（ｃ２）７０〜９０重量％、及びブテン−１系重合体（ｃ３）１０〜３０重量％を含有する樹脂層（Ｃ）とを、（Ａ）／（Ｂ）／（Ｃ）の順、又は（Ａ）／（Ｂ）／（Ａ）／（Ｃ）の順に積層したことを特徴とする共押出多層フィルム及び該フィルムを用いた包装材を提供するものである。 That is, the present invention relates to a resin layer (A) comprising a low density polyethylene (a1) and / or a linear low density polyethylene resin (a2), a low density polyethylene (b1) and / or a linear low density polyethylene resin. (B2) 70 to 90% by mass of resin layer (B) containing 10 to 30% by mass of cyclic olefin resin (b3), low density polyethylene resin (c1) and / or linear low density polyethylene resin ( c2) A resin layer (C) containing 70 to 90% by weight and 10 to 30% by weight of a butene-1 polymer (c3), in the order of (A) / (B) / (C), or ( A coextruded multilayer film characterized by being laminated in the order of A) / (B) / (A) / (C) and a packaging material using the film.
本発明の共押出多層フィルムは、縦方向及び横方向ともに容易に直線で引き裂くことができる易カット性と、ヒートシール部を容易に引き剥がすことができるイージーピール性との２種の易開封性を有するため、社会的弱者にも簡単に開封が可能な包装材が提供できる。また、優れた二次成形性、屈曲による耐ピンホール性も有する。したがって、本発明の共押出多層フィルムは、食品、薬品、医療器具、工業部品、雑貨、雑誌等を包装する包装材に好適である。特に、易カット性とイージーピール性との２種の易開封性を有することから、短時間に確実に開封できるため、医療器具用の包装材として非常に有用である。 The co-extruded multilayer film of the present invention has two types of easy-opening properties: easy cutability that allows easy tearing in both the vertical and horizontal directions, and easy peelability that allows easy peeling of the heat seal portion. Therefore, it is possible to provide a packaging material that can be easily opened even by a socially vulnerable person. It also has excellent secondary moldability and resistance to pinholes caused by bending. Therefore, the coextruded multilayer film of the present invention is suitable for a packaging material for packaging foods, medicines, medical instruments, industrial parts, miscellaneous goods, magazines and the like. In particular, since it has two types of easy-openability, easy-cut property and easy-peel property, it can be reliably opened in a short time, and is therefore very useful as a packaging material for medical instruments.
本発明の共押出多層フィルムの樹脂層（Ａ）、（Ｂ）及び（Ｃ）で用いる低密度ポリエチレン（ａ１）、（ｂ１）及び（ｃ１）は、高圧ラジカル重合法で得られる分岐状低密度ポリエチレンであれば良く、好ましくは高圧ラジカル重合法によりエチレンを単独重合した分岐状低密度ポリエチレンである。このような低密度ポリエチレンは機械強度が弱いため、他のオレフィン樹脂と比べて比較的もろく引き裂き性が良好になる上、環状オレフィン系樹脂（ｂ２）との相溶性も良いため、ブレンドした際の透明性も維持することができる。さらに、接着性樹脂や接着剤等を使用することなく、樹脂層（Ａ）と樹脂層（Ｂ）との層間の接着強度も保持でき、柔軟性も有しているため、耐ピンホール性も良好となる。 The low density polyethylene (a1), (b1) and (c1) used in the resin layers (A), (B) and (C) of the coextruded multilayer film of the present invention are branched low density obtained by a high pressure radical polymerization method. Polyethylene may be used, and branched low-density polyethylene obtained by homopolymerizing ethylene by a high-pressure radical polymerization method is preferable. Since such low density polyethylene has low mechanical strength, it is relatively brittle compared to other olefin resins and has good tearability, and also has good compatibility with the cyclic olefin resin (b2). Transparency can also be maintained. Furthermore, the adhesive strength between the resin layer (A) and the resin layer (B) can be maintained without using an adhesive resin or an adhesive, and since it has flexibility, it has pinhole resistance. It becomes good.
前記低密度ポリエチレンは、密度が０．９００〜０．９３５ｇ／ｃｍ３であるものが好ましく、０．９１５〜０．９３０ｇ／ｃｍ３のものがより好ましい。密度がこの範囲であれば、適度な剛性を有し、耐ピンホール性等の機械強度も優れ、フィルム成膜性、押出適性が向上する。 The low density polyethylene is preferably one density of 0.900~0.935g / cm 3, it is more preferred 0.915~0.930g / cm 3. If the density is within this range, it has appropriate rigidity, excellent mechanical strength such as pinhole resistance, and film film formability and extrusion suitability are improved.
また、前記低密度ポリエチレンは、メルトフローレート（ＪＩＳ Ｋ７２１０に準拠して、１９０℃、２１．１８Ｎで測定した値；以下、「ＭＦＲ」という。）が０．１〜１０ｇ／１０分であるものが好ましく、０．３〜８．０ｇ／１０分のものがより好ましく、０．８〜６．０ｇ／１０分のものが特に好ましい。ＭＦＲがこの範囲であれば、フィルムの押出成形性が向上する。 The low density polyethylene has a melt flow rate (measured at 190 ° C. and 21.18 N in accordance with JIS K7210; hereinafter referred to as “MFR”) of 0.1 to 10 g / 10 min. Is preferable, 0.3 to 8.0 g / 10 min is more preferable, and 0.8 to 6.0 g / 10 min is particularly preferable. When the MFR is within this range, the extrusion moldability of the film is improved.
さらに、前記低密度ポリエチレンは、メルトテンション（溶融張力；以下、「ＭＴ」という。）が４〜１５であるものが好ましく、５〜１３のものがより好ましい。ＭＴがこの範囲であれば、二次成形性、耐ピンホール性が向上する。なお、このＭＴは、メルトテンションテスター（例えば、株式会社東洋精機製作所製のもの）を用いて測定した値で、同装置内に低密度ポリエチレンを１９０℃に加熱後、この樹脂を２ｍｍφのノズルから０．７５ｍｌ／分で２３℃の雰囲気下で押出ストランドとし、このストランドを９０ｃｍのエアーギャップをつけて２５〜６０ｍ／分の速度で引き取る際の張力を測定することによって得られる。 Further, the low density polyethylene preferably has a melt tension (melt tension; hereinafter referred to as “MT”) of 4 to 15, more preferably 5 to 13. When MT is within this range, secondary formability and pinhole resistance are improved. The MT is a value measured using a melt tension tester (for example, manufactured by Toyo Seiki Seisakusho Co., Ltd.). After the low-density polyethylene is heated to 190 ° C. in the same apparatus, the resin is discharged from a 2 mmφ nozzle. It is obtained by forming an extruded strand at 0.75 ml / min in an atmosphere of 23 ° C., and measuring the tension when the strand is drawn at a speed of 25 to 60 m / min with an air gap of 90 cm.
本発明の共押出多層フィルムの樹脂層（Ａ）、（Ｂ）及び（Ｃ）に前記低密度ポリエチレンに代え、直鎖状低密度ポリエチレンを用いると、耐ピンホール性やホットタック性を向上することができ、さらに、各樹脂層を薄膜化しても十分な機械強度を得ることができ、フィルム剛性を向上することができる。この樹脂層（Ａ）、（Ｂ）及び（Ｃ）に用いる直鎖状低密度ポリエチレン（ａ２）、（ｂ２）及び（ｃ２）としては、直鎖状低密度ポリエチレンの中でもメタロセン触媒により製造されたエチレン−ブテン−１共重合体が好ましい。通常のグレードの直鎖状低密度ポリエチレンを用いた場合、前記低密度ポリエチレンと比較して機械強度が高いため、易カット性が不十分となる場合があるが、このメタロセン触媒により製造されたエチレン−ブテン−１共重合体を用いることで、十分な易カット性を得ることができる。前記メタロセン触媒により製造されたエチレン−ブテン−１共重合は、密度が０．９１６〜０．９５０ｇ／ｃｍ３のものが好ましく、０．９１９〜０．９４０ｇ／ｃｍ３のものがより好ましい。密度がこの範囲であれば、十分な機械強度（耐衝撃性）が得られ、フィルム剛性が十分なものとなる。また、ＭＦＲ（１９０℃、２１．１８Ｎ）は、２〜１０ｇ／１０分のものが好ましく、３〜７ｇ／１０分のものがより好ましい。ＭＦＲがこの範囲であれば、フィルムの押出成形性が向上する。さらに、前記メタロセン触媒により製造されたエチレン−ブテン−１共重合体中のブテン−１単量体の含有量は、０．５〜１０モル％が好ましく、１〜５モル％がより好ましい。 When linear low density polyethylene is used instead of the low density polyethylene in the resin layers (A), (B) and (C) of the coextruded multilayer film of the present invention, pinhole resistance and hot tack resistance are improved. Furthermore, even if each resin layer is thinned, sufficient mechanical strength can be obtained, and film rigidity can be improved. The linear low density polyethylene (a2), (b2) and (c2) used for the resin layers (A), (B) and (C) were produced by a metallocene catalyst among linear low density polyethylenes. An ethylene-butene-1 copolymer is preferred. When a normal grade linear low density polyethylene is used, the mechanical strength is higher than that of the low density polyethylene, so that the easy-cut property may be insufficient, but the ethylene produced by this metallocene catalyst -By using a butene-1 copolymer, sufficient easy cutting properties can be obtained. The ethylene-butene-1 copolymer produced with the metallocene catalyst preferably has a density of 0.916 to 0.950 g / cm 3 , more preferably 0.919 to 0.940 g / cm 3 . When the density is within this range, sufficient mechanical strength (impact resistance) is obtained, and the film rigidity is sufficient. The MFR (190 ° C., 21.18N) is preferably 2 to 10 g / 10 minutes, more preferably 3 to 7 g / 10 minutes. When the MFR is within this range, the extrusion moldability of the film is improved. Further, the content of the butene-1 monomer in the ethylene-butene-1 copolymer produced by the metallocene catalyst is preferably 0.5 to 10 mol%, more preferably 1 to 5 mol%.
また、本発明の共押出多層フィルムの樹脂層（Ａ）、（Ｂ）及び（Ｃ）において、前記低密度ポリエチレンと直鎖状低密度ポリエチレンとを併用しても構わない。低密度ポリエチレンと直鎖状低密度ポリエチレンとを併用した場合、易カット性と、耐ピンホール性、ホットタック性及びフィルム剛性を各々向上することができ好ましい。低密度ポリエチレン（以下、「ＬＤＰＥ」という。）と直鎖状低密度ポリエチレン（以下、「ＬＬＤＰＥ」という。）とを併用する場合の両者の含有比率は、質量基準でＬＤＰＥ：ＬＬＤＰＥ＝９５：５〜４０：６０の範囲が好ましく、９０：１０〜５０：５０の範囲がより好ましい。ＬＤＰＥとＬＬＤＰＥとの含有比率がこの範囲であれば、易カット性、耐ピンホール性、ホットタック性及びフィルム剛性が向上する。 In the resin layers (A), (B) and (C) of the coextruded multilayer film of the present invention, the low density polyethylene and the linear low density polyethylene may be used in combination. When low density polyethylene and linear low density polyethylene are used in combination, it is possible to improve easy cutability, pinhole resistance, hot tack property and film rigidity, respectively. When the low density polyethylene (hereinafter referred to as “LDPE”) and the linear low density polyethylene (hereinafter referred to as “LLDPE”) are used in combination, the content ratio of both is LDPE: LLDPE = 95: 5. The range of -40: 60 is preferable, and the range of 90: 10-50: 50 is more preferable. When the content ratio of LDPE and LLDPE is within this range, easy-cut property, pinhole resistance, hot tack property and film rigidity are improved.
本発明の共押出多層フィルムの樹脂層（Ｂ）で用いる環状オレフィン系樹脂（ｂ２）としては、例えば、ノルボルネン系重合体、ビニル脂環式炭化水素重合体、環状共役ジエン重合体等が挙げられる。これらの中でも、ノルボルネン系重合体が好ましい。また、ノルボルネン系重合体としては、ノルボルネン系単量体の開環重合体（以下、「ＣＯＰ」という。）、ノルボルネン系単量体とエチレン等のオレフィンを共重合したノルボルネン系共重合体（以下、「ＣＯＣ」という。）等が挙げられる。さらに、ＣＯＰ及びＣＯＣの水素添加物は、特に好ましい。また、環状オレフィン系樹脂（ｂ２）の重量平均分子量は、５，０００〜５００，０００が好ましく、より好ましくは７，０００〜３００，０００である。 Examples of the cyclic olefin resin (b2) used in the resin layer (B) of the coextruded multilayer film of the present invention include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, a cyclic conjugated diene polymer, and the like. . Among these, norbornene-based polymers are preferable. The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Furthermore, COP and COC hydrogenates are particularly preferred. In addition, the weight average molecular weight of the cyclic olefin resin (b2) is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
前記ノルボルネン系重合体と原料となるノルボルネン系単量体は、ノルボルネン環を有する脂環族系単量体である。このようなノルボルネン系単量体としては、例えば、
ノルボルネン、テトラシクロドデセン、エチリデンノルボルネン、ビニルノルボルネン、エチリデテトラシクロドデセン、ジシクロペンタジエン、ジメタノテトラヒドロフルオレン、フェニルノルボルネン、メトキシカルボニルノルボルネン、メトキシカルボニルテトラシクロドデセン等が挙げられる。これらのノルボルネン系単量体は、単独で用いても、２種以上を併用しても良い。
The norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring. As such a norbornene-based monomer, for example,
Examples thereof include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, methoxycarbonyltetracyclododecene and the like. These norbornene monomers may be used alone or in combination of two or more.
前記ノルボルネン系共重合体（ＣＯＣ）は、前記ノルボルネン系単量体と共重合可能なオレフィンとを共重合したものであり、このようなオレフィンとしては、例えば、エチレン、プロピレン、１−ブテン等の炭素原子数２〜２０個を有するオレフィン；シクロブテン、シクロペンテン、シクロヘキセン等のシクロオレフィン；１，４−ヘキサジエン等の非共役ジエンなどが挙げられる。これらのオレフィンは、それぞれ単独でも、２種類以上を併用することもできる。 The norbornene-based copolymer (COC) is obtained by copolymerizing an olefin copolymerizable with the norbornene-based monomer. Examples of such olefin include ethylene, propylene, and 1-butene. Examples thereof include olefins having 2 to 20 carbon atoms; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; non-conjugated dienes such as 1,4-hexadiene. These olefins can be used alone or in combination of two or more.
また、前記ノルボルネン系共重合体（ＣＯＣ）中のノルボルネン系単量体の含有比率は、４０〜９０モル％が好ましく、より好ましくは５０〜８０モル％である。含有比率がこの範囲にあれば、フィルム剛性、引き裂き性、加工安定性が向上する。 In addition, the content ratio of the norbornene monomer in the norbornene copolymer (COC) is preferably 40 to 90 mol%, more preferably 50 to 80 mol%. If the content ratio is in this range, the film rigidity, tearability, and processing stability are improved.
前記環状オレフィン系樹脂（ｂ２）として用いることができる市販品としては、ノルボルネン系モノマーの開環重合体（ＣＯＰ）、例えば、日本ゼオン株式会社製「ゼオノア（ＺＥＯＮＯＲ）」等が挙げられ、ノルボルネン系付加重合体（ＣＯＣ）、例えば、三井化学株式会社製「アペル」、チコナ（ＴＩＣＯＮＡ）社製「トパス（ＴＯＰＡＳ）」等が挙げられる。 Examples of commercially available products that can be used as the cyclic olefin-based resin (b2) include ring-opening polymers (COP) of norbornene-based monomers, such as “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and norbornene-based resins. Addition polymers (COC), for example, “Apel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by TICONA, and the like can be mentioned.
前記樹脂層（Ｂ）中の前記低密度ポリエチレン（ｂ１）及び／又は直鎖状低密度ポリエチレン（ｂ２）と、前記環状ポリオレフィン系樹脂（ｂ３）との含有比率は、質量基準で（ｂ１）及び／又は（ｂ２）：（ｂ３）＝７０：３０〜９０：１０であるが、より好ましくは（ｂ１）及び／又は（ｂ２）：（ｂ３）＝８０：２０〜９０：１０である。各樹脂の含有比率がこの範囲であれば、透明性が向上し、縦方向及び横方向の易カット性、樹脂層（Ａ）、（Ｃ）との間の層間接着強度が向上するので好ましい。 The content ratio of the low-density polyethylene (b1) and / or linear low-density polyethylene (b2) in the resin layer (B) and the cyclic polyolefin-based resin (b3) is (b1) and / B (b2) :( b3) = 70: 30 to 90:10, more preferably (b1) and / or (b2) :( b3) = 80: 20 to 90:10. If the content ratio of each resin is within this range, the transparency is improved, and the ease of cutting in the vertical and horizontal directions and the interlayer adhesive strength between the resin layers (A) and (C) are improved.
本発明の共押出多層フィルムの樹脂層（Ｃ）は、ヒートシール層となるが、樹脂層（Ｃ）に用いるブテン−１系重合体（ｃ３）は、ブテン−１の単独重合体又はブテン−１を主成分として、これにエチレン又はプロピレンを共重合した樹脂である。ブテン−１系重合体中のブテン−１単量体の含有量としては、６０〜１００モル％が好ましく、７０〜１００モル％がより好ましい。また、ブテン−１系重合体（ｃ３）の融点は、７０〜１２０℃の範囲が好ましい。融点がこの範囲であれば、フィルム同士のブロッキングが防止でき、低温ヒートシール性に優れる。 The resin layer (C) of the coextruded multilayer film of the present invention serves as a heat seal layer, but the butene-1 polymer (c3) used for the resin layer (C) is a butene-1 homopolymer or butene- A resin having 1 as a main component and copolymerized with ethylene or propylene. As content of the butene-1 monomer in a butene-1 type polymer, 60-100 mol% is preferable and 70-100 mol% is more preferable. Further, the melting point of the butene-1 polymer (c3) is preferably in the range of 70 to 120 ° C. If melting | fusing point is this range, blocking of films can be prevented and it is excellent in low temperature heat-sealing property.
前記樹脂層（Ｃ）中の前記低密度ポリエチレン（ｃ１）及び／又は直鎖状低密度ポリエチレン（ｃ２）と、前記ポリブテン−１（ｃ３）との含有比率は、質量基準で（ｃ１）及び／又は（ｃ２）：（ｃ３）＝７０：３０〜９０：１０であるが、より好ましくは（ｃ１）及び／又は（ｃ２）：（ｃ３）＝７５：２５〜９０：１０である。各樹脂の含有比率がこの範囲であれば、透明性が向上し、適度なヒートシール強度となるため、イージーピール性を付与することができ好ましい。 The content ratio of the low density polyethylene (c1) and / or the linear low density polyethylene (c2) and the polybutene-1 (c3) in the resin layer (C) is (c1) and / or Or (c2) :( c3) = 70: 30 to 90:10, more preferably (c1) and / or (c2) :( c3) = 75: 25 to 90:10. If the content ratio of each resin is within this range, transparency is improved and an appropriate heat seal strength is obtained.
本発明の共押出多層フィルムは、前記樹脂層（Ａ）、（Ｂ）及び（Ｃ）を、（Ａ）／（Ｂ）／（Ｃ）の順で積層した３層構成の多層フィルム、又は（Ａ）／（Ｂ）／（Ａ）／（Ｃ）の順で積層した４層構成の多層フィルムである。この多層フィルム中の前記樹脂層（Ｂ）の厚さは、共押出多層フィルムの厚さの２０〜６０％が好ましく、２０〜５０％がより好ましい。共押出多層フィルムの厚さに対する樹脂層（Ｂ）の厚さの比率がこの範囲であれば、透明性、引き裂き性、耐ピンホール性が向上する。 The coextruded multilayer film of the present invention is a multilayer film having a three-layer structure in which the resin layers (A), (B) and (C) are laminated in the order of (A) / (B) / (C), or ( A multilayer film having a four-layer structure laminated in the order of A) / (B) / (A) / (C). The thickness of the resin layer (B) in this multilayer film is preferably 20 to 60%, more preferably 20 to 50%, of the thickness of the coextruded multilayer film. When the ratio of the thickness of the resin layer (B) to the thickness of the coextruded multilayer film is within this range, the transparency, tearability, and pinhole resistance are improved.
さらに、本発明の共押出多層フィルムは、厚さが５０〜３００μｍのものが好ましい。多層フィルムの厚さが８０μｍ以上であれば、優れた二次成形性が得られる。また、多層フィルムの厚さが５０〜８０μｍの範囲では、樹脂層（Ｃ）同士をヒートシールさせた袋状の包装材として使用できる。さらに、本発明の共押出多層フィルムは、その厚さが１００〜３００μｍの厚膜であっても、直線カット性及び引き裂き性に優れる。 Furthermore, the coextruded multilayer film of the present invention preferably has a thickness of 50 to 300 μm. If the thickness of the multilayer film is 80 μm or more, excellent secondary formability can be obtained. Moreover, in the range whose thickness of a multilayer film is 50-80 micrometers, it can be used as a bag-shaped packaging material which heat-sealed resin layers (C). Furthermore, even if the coextruded multilayer film of the present invention is a thick film having a thickness of 100 to 300 μm, it is excellent in linear cut property and tear property.
前記樹脂層（Ａ）、（Ｂ）及び（Ｃ）には、必要に応じて、防曇剤、帯電防止剤、熱安定剤、造核剤、酸化防止剤、滑剤、アンチブロッキング剤、離型剤、紫外線吸収剤、着色剤等の成分を本発明の目的を損なわない範囲で添加することができる。特に、フィルム成形時の加工適性、充填機の包装適性を付与するため、樹脂層（Ａ）及び（Ｃ）の摩擦係数を１．５以下、中でも１．２以下にすることが好ましいので、樹脂層（Ａ）及び（Ｃ）には、滑剤やアンチブロッキング剤を適宜添加することが好ましい。 In the resin layers (A), (B) and (C), an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent are optionally provided. Components such as an agent, an ultraviolet absorber and a colorant can be added within a range that does not impair the object of the present invention. In particular, the resin layer (A) and (C) preferably have a friction coefficient of 1.5 or less, more preferably 1.2 or less in order to impart processing suitability during film forming and packaging suitability of the filling machine. It is preferable to add a lubricant or an antiblocking agent to the layers (A) and (C) as appropriate.
本発明の共押出多層フィルムの製造方法としては、特に限定されないが、例えば、樹脂層（Ａ）に用いる低密度ポリエチレン（ａ１）及び／又は直鎖状低密度ポリエチレン（ａ２）と、樹脂層（Ｂ）に用いる低密度ポリエチレン（ｂ１）及び／又は直鎖状低密度ポリエチレン（ｂ２）、及び環状オレフィン系樹脂（ｂ３）と、樹脂層（Ｃ）に用いる低密度ポリエチレン樹脂（ｃ１）及び／又は直鎖状低密度ポリエチレン樹脂（ｃ２）、及びブテン−１系重合体（ｃ３）とを、それぞれ別の押出機で加熱溶融させ、共押出多層ダイス法やフィードブロック法等の方法により溶融状態で（Ａ）／（Ｂ）／（Ｃ）の順、又は（Ａ）／（Ｂ）／（Ａ）／（Ｃ）の順で積層した後、インフレーションやＴダイ・チルロール法等によりフィルム状に成形する共押出法が挙げられる。この共押出法は、各層の厚さの比率を比較的自由に調整することが可能で、衛生性に優れ、コストパフォーマンスにも優れた多層フィルムが得られるので好ましい。さらに、本発明で用いる低密度ポリエチレン樹脂と環状オレフィン樹脂との軟化点（融点）の差が大きいため、相分離やゲルを生じることがある。このような相分離やゲルの発生を抑制するためには、比較的高温で溶融押出を行うことができるＴダイ・チルロール法が好ましい。 Although it does not specifically limit as a manufacturing method of the coextrusion multilayer film of this invention, For example, the low density polyethylene (a1) and / or linear low density polyethylene (a2) used for a resin layer (A), and a resin layer ( B) low density polyethylene (b1) and / or linear low density polyethylene (b2) and cyclic olefin resin (b3) used for the resin layer (C) and / or low density polyethylene resin (c1) and / or The linear low density polyethylene resin (c2) and the butene-1 polymer (c3) are heated and melted in separate extruders, and are melted by a method such as a coextrusion multilayer die method or a feed block method. After laminating in the order of (A) / (B) / (C) or in the order of (A) / (B) / (A) / (C), it is formed into a film by inflation, T-die chill roll method, etc. You Coextrusion methods. This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a multilayer film excellent in hygiene and cost performance can be obtained. Furthermore, since the difference in softening point (melting point) between the low density polyethylene resin and the cyclic olefin resin used in the present invention is large, phase separation or gel may occur. In order to suppress the occurrence of such phase separation and gel, the T-die / chill roll method capable of performing melt extrusion at a relatively high temperature is preferable.
本発明の共押出多層フィルムは、上記の製造方法によって、実質的に無延伸の多層フィルムとして得られるため、真空成形による深絞り成形等の二次成形が可能となる。 Since the coextruded multilayer film of the present invention is obtained as a substantially unstretched multilayer film by the above production method, secondary molding such as deep drawing by vacuum molding becomes possible.
本発明の共押出多層フィルムをシーラントフィルムとして用い、樹脂層（Ａ）上に接着性樹脂や接着剤を介して基材をラミネートしてラミネートフィルムとすることもできる。このラミネートフィルムに用いる基材としては、易カット性を損なわないものであれば特に制限はないが、例えば、二軸延伸ポリプロピレン（ＯＰＰ）、エチレンビニルアルコール共重合体（ＥＶＯＨ）を中心層とした共押出二軸延伸ポリプロピレン、二軸延伸エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリ塩化ビニリデン（ＰＶＤＣ）をコートした共押出二軸延伸ポリプロピレン、二軸延伸ナイロン、二軸延伸ポリエチレンテレフタレート、アルミニウム箔等が挙げられる。接着方法としては、ドライラミネーション、ウェットラミネーション、ノンソルベントラミネーション、押出ラミネーション等の方法が挙げられる。 The coextruded multilayer film of the present invention can be used as a sealant film, and a substrate can be laminated on the resin layer (A) via an adhesive resin or adhesive to form a laminate film. The base material used for the laminate film is not particularly limited as long as it does not impair easy-cutability. For example, biaxially stretched polypropylene (OPP) and ethylene vinyl alcohol copolymer (EVOH) are used as the central layer. Coextruded biaxially oriented polypropylene, biaxially oriented ethylene vinyl alcohol copolymer (EVOH), coextruded biaxially oriented polypropylene coated with polyvinylidene chloride (PVDC), biaxially oriented nylon, biaxially oriented polyethylene terephthalate, aluminum foil, etc. Is mentioned. Examples of the bonding method include dry lamination, wet lamination, non-solvent lamination, extrusion lamination, and the like.
前記ドライラミネーションで用いる接着剤としては、例えば、ポリエーテル−ポリウレタン系接着剤、ポリエステル−ポリウレタン系接着剤等が挙げられる。 Examples of the adhesive used in the dry lamination include a polyether-polyurethane adhesive and a polyester-polyurethane adhesive.
さらに、印刷インキとの接着性、ラミネート適性を向上させるため、前記樹脂層（Ａ）に表面処理を施すことが好ましい。このような表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線処理等の表面酸化処理、あるいはサンドブラスト等の表面凹凸処理を挙げることができるが、好ましくはコロナ処理である。 Furthermore, in order to improve the adhesiveness with the printing ink and the suitability for lamination, it is preferable to subject the resin layer (A) to a surface treatment. Examples of such surface treatment include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona treatment is preferable.
本発明の共押出多層フィルムからなる包装材としては、食品、薬品、医療器具、工業部品、雑貨、雑誌等の用途に用いる包装袋、包装容器等が挙げられる。 Examples of the packaging material comprising the coextruded multilayer film of the present invention include packaging bags and packaging containers used for foods, medicines, medical instruments, industrial parts, miscellaneous goods, magazines and the like.
前記包装袋は、本発明の共押出多層フィルムの樹脂層（Ｃ）をヒートシール層として、樹脂層（Ｃ）同士を重ねてヒートシールすることにより形成した包装袋である。２枚の当該共押出多層フィルムを所望とする包装袋の大きさに切り出して、それらを重ねて３辺をヒートシールして袋状にした後、ヒートシールをしていない１辺から内容物を充填した後、ヒートシールして密封することで包装袋として用いることができる。また、１枚の当該共押出多層フィルムを用いて、ピロー包装の形態でも用いることができる。さらに、樹脂層（Ｃ）とヒートシール可能な別のフィルムを重ねてヒートシールすることにより包装袋を形成することも可能である。その際、使用する別のフィルムとしては、比較的機械強度の弱いＬＤＰＥ、ＥＶＡ等のフィルムを用いることができる。また、ＬＤＰＥ、ＥＶＡ等のフィルムと、比較的引き裂き性の良い延伸フィルム、例えば、二軸延伸ポリエチレンテレフタレートフィルム（ＯＰＥＴ）、二軸延伸ポリプロピレンフィルム（ＯＰＰ）等とを貼り合わせたラミネートフィルムも用いることができる。 The packaging bag is a packaging bag formed by heat-sealing the resin layers (C) by using the resin layer (C) of the coextruded multilayer film of the present invention as a heat seal layer. Cut the two coextruded multilayer films into the desired size of the packaging bag, overlap them and heat-seal three sides to form a bag, and then remove the contents from one side that is not heat-sealed. After filling, it can be heat sealed and used as a packaging bag. Moreover, it can be used also in the form of pillow packaging using a single sheet of the coextruded multilayer film. Furthermore, it is also possible to form a packaging bag by heat-sealing another resin layer (C) and another heat-sealable film. At that time, as another film to be used, a film such as LDPE or EVA having relatively low mechanical strength can be used. In addition, a laminate film in which a film such as LDPE or EVA and a stretched film having relatively good tearability, for example, a biaxially stretched polyethylene terephthalate film (OPET), a biaxially stretched polypropylene film (OPP), or the like, is used. Can do.
また、前記包装容器としては、本発明の共押出多層フィルムを二次成形することにより得られる深絞り成形品（上部に開口部がある底材）が挙げられ、代表的なものとしてブリスターパックの底材が挙げられる。この底材を密封する蓋材は、底材とヒートシールできるものであれば特に材質は問わないが、蓋材と底材を同時に引き裂いて開封できることから、本発明の共押出多層フィルムを蓋材として用いることが好ましい。 The packaging container includes a deep-drawn molded product (bottom material having an opening at the top) obtained by secondary molding of the coextruded multilayer film of the present invention. A bottom material is mentioned. The lid material for sealing the bottom material is not particularly limited as long as it can be heat-sealed with the bottom material. However, since the lid material and the bottom material can be simultaneously torn and opened, the coextruded multilayer film of the present invention is covered with the lid material. It is preferable to use as.
上記の二次成形方法としては、例えば、真空成形法、圧空成形法、真空圧空成形法等が挙げられる。これらの中でも、フィルムあるいはシートを包装機上にてインラインで成形し、内容物を充填できるため真空成形が好ましい。 Examples of the secondary forming method include a vacuum forming method, a pressure forming method, and a vacuum / pressure forming method. Among these, vacuum forming is preferable because a film or sheet can be formed in-line on a packaging machine and filled with the contents.
本発明の共押出多層フィルムを用いた包装材には、初期の引き裂き強度を弱め、開封性を向上するため、シール部にＶノッチ、Ｉノッチ、ミシン目、微多孔などの任意の引き裂き開始部を形成すると好ましい。 The packaging material using the coextruded multilayer film of the present invention has an arbitrary tear start portion such as a V-notch, an I-notch, a perforation, and a micro-porosity in the seal portion in order to weaken the initial tear strength and improve the openability. Is preferably formed.
次に、実施例及び比較例を挙げて本発明をより詳しく説明する。 Next, the present invention will be described in more detail with reference to examples and comparative examples.
（実施例１）
樹脂層（Ａ）用樹脂として、低密度ポリエチレン（宇部丸善ポリエチレン株式会社製「ＵＢＥポリエチレン Ｆ１０９」、密度：０．９１８ｇ／ｃｍ３、ＭＦＲ：２ｇ／１０分（１９０℃、２１．１８Ｎ）、ＭＴ：１０ｇ；以下、「ＬＤＰＥ」という。）を用い、樹脂層（Ｂ）用樹脂として、ＬＤＰＥ８０質量部及び環状オレフィン系共重合体（日本ゼオン株式会社製「ゼオノア １０６０Ｒ」、ＭＦＲ：６０ｇ／１０分（２８０℃、２１．１８Ｎ）、ガラス転移温度：１００℃；以下、「ＣＯＰ」という。）２０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＤＰＥ９０質量部及びポリブテン−１（ＢＡＳＥＬＬ社製「８２４０」、密度：０．９１ｇ／ｃｍ３、ＭＦＲ：２ｇ／１０分（１９０℃、２１．１８Ｎ）；以下、「ＰＢ−１」という。）１０質量部の混合樹脂を用いた。
Example 1
As a resin for the resin layer (A), low density polyethylene (“UBE polyethylene F109” manufactured by Ube Maruzen Polyethylene Co., Ltd., density: 0.918 g / cm 3 , MFR: 2 g / 10 min (190 ° C., 21.18 N), MT : 10 g; hereinafter referred to as “LDPE”), as resin for the resin layer (B), 80 parts by mass of LDPE and a cyclic olefin copolymer (“ZEONOR 1060R” manufactured by Nippon Zeon Co., Ltd., MFR: 60 g / 10 minutes) (280 ° C., 21.18 N), glass transition temperature: 100 ° C .; hereinafter referred to as “COP”) Using 20 parts by mass of mixed resin, as resin for resin layer (C), 90 parts by mass of LDPE and polybutene-1 ( BASELL Inc. "8240", density: 0.91g / cm 3, MFR: 2g / 10 min (190 ℃, 21.18N); hereinafter, "PB 1 "hereinafter.) With 10 parts by weight mixed resin.
これらの樹脂をそれぞれ、樹脂層（Ａ）用押出機（口径５０ｍｍ）、樹脂層（Ｂ）用押出機（口径５０ｍｍ）及び樹脂層（Ｃ）用押出機（口径４０ｍｍ）に供給して２００〜２３０℃で溶融した後、フィードブロックを有するＴダイ・チルロール法の共押出多層フィルム製造装置（フィードブロック及びＴダイ温度：２５０℃）にそれぞれ供給して共溶融押出を行って、フィルムの層構成が（Ａ）／（Ｂ）／（Ｃ）の３層構成で、各層の厚さが６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）である共押出多層フィルムを得た。 These resins are supplied to an extruder for a resin layer (A) (caliber 50 mm), an extruder for a resin layer (B) (caliber 50 mm) and an extruder for a resin layer (C) (caliber 40 mm), respectively. After melting at 230 ° C., each film is supplied to a T-die / chill roll co-extruded multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block to perform co-melt extrusion, and the layer structure of the film Was a three-layer structure of (A) / (B) / (C), and a coextruded multilayer film having a thickness of 60 μm / 50 μm / 10 μm (total of 120 μm) was obtained.
（実施例２）
樹脂層（Ｃ）用樹脂として、ＬＤＰＥ７０質量部及びＰＢ−１ ３０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ａ）＝６０μｍ／３０μｍ／３０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Example 2)
The thickness of each layer of the film is (A) / (B) in the same manner as in Example 1 except that a mixed resin of 70 parts by mass of LDPE and 30 parts by mass of PB-1 was used as the resin for the resin layer (C). / (A) = 60 μm / 30 μm / 30 μm (total 120 μm) was prepared as a co-extruded multilayer film to obtain a co-extruded multilayer film.
（実施例３）
樹脂層（Ａ）用樹脂として、メタロセンで触媒により製造されたエチレン−ブテン−１共重合体（宇部丸善ポリエチレン株式会社製「ＺＭ０３９」、密度：０．９３ｇ／ｃｍ３、ＭＦＲ：４ｇ／１０分（１９０℃、２１．１８Ｎ）；以下、「ＬＬＤＰＥ」という。）を用い、樹脂層（Ｂ）用樹脂として、ＬＬＤＰＥ８０質量部及びＣＯＰ２０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＬＤＰＥ７０質量部及びＰＢ−１ ３０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Example 3)
As a resin for the resin layer (A), an ethylene-butene-1 copolymer produced by a metallocene catalyst (“ZM039” manufactured by Ube Maruzen Polyethylene Co., Ltd., density: 0.93 g / cm 3 , MFR: 4 g / 10 minutes) (190 ° C., 21.18 N); hereinafter referred to as “LLDPE”), as a resin for the resin layer (B), a mixed resin of 80 parts by mass of LLDPE and 20 parts by mass of COP is used as a resin for the resin layer (C). The thickness of each layer of the film was (A) / (B) / (C) = 60 μm / 50 μm in the same manner as in Example 1 except that 70 parts by mass of LLDPE and 30 parts by mass of PB-1 were used. A coextruded multilayer film was prepared so as to be / 10 μm (120 μm in total) to obtain a coextruded multilayer film.
（実施例４）
樹脂層（Ａ）用樹脂として、ＬＤＰＥ７０重量部とＬＬＤＰＥ３０重量部の混合樹脂を用い、樹脂層（Ｂ）用樹脂として、ＬＤＰＥ５０重量部、ＬＬＤＰＥ３０質量部及びＣＯＰ２０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＤＰＥ７０重量部及びＰＢ−１ ３０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／３０μｍ／３０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
Example 4
As resin for resin layer (A), a mixed resin of 70 parts by weight of LDPE and 30 parts by weight of LLDPE is used, and as a resin for resin layer (B), a mixed resin of 50 parts by weight of LDPE, 30 parts by weight of LLDPE and 20 parts by weight of COP is used. The thickness of each layer of the film is (A) / (B) / () in the same manner as in Example 1 except that a mixed resin of 70 parts by weight of LDPE and 30 parts by weight of PB-1 was used as the resin for (C). C) = 60 μm / 30 μm / 30 μm (a total of 120 μm) was prepared as a coextruded multilayer film to obtain a coextruded multilayer film.
（実施例５）
樹脂層（Ａ）用樹脂として、ＬＤＰＥを用い、樹脂層（Ｂ）用樹脂として、ＬＤＰＥ８０質量部及びＣＯＰ２０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＤＰＥ７０質量部及びＰＢ−１ ３０質量部の混合樹脂を用いた。
(Example 5)
LDPE is used as the resin for the resin layer (A), 80 parts by mass of LDPE and 20 parts by mass of COP are used as the resin for the resin layer (B), and 70 parts by mass of LDPE and PB- are used as the resin for the resin layer (C). 1 30 parts by mass of mixed resin was used.
これらの樹脂をそれぞれ、樹脂層（Ａ）用押出機（口径５０ｍｍ）、樹脂層（Ｂ）用押出機（口径５０ｍｍ）及び樹脂層（Ｃ）用押出機（口径４０ｍｍ）に供給して２００〜２３０℃で溶融した後、フィードブロックを有するＴダイ・チルロール法の共押出多層フィルム製造装置（フィードブロック及びＴダイ温度：２５０℃）にそれぞれ供給して共溶融押出を行って、フィルムの層構成が（Ａ）／（Ｂ）／（Ａ）／（Ｃ）の４層構成で、各層の厚さが６０μｍ／３０μｍ／１０μｍ／２０μｍ（合計１２０μｍ）である共押出多層フィルムを得た。 These resins are supplied to an extruder for a resin layer (A) (caliber 50 mm), an extruder for a resin layer (B) (caliber 50 mm) and an extruder for a resin layer (C) (caliber 40 mm), respectively. After melting at 230 ° C., each film is supplied to a T-die / chill roll co-extruded multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block to perform co-melt extrusion, and the layer structure of the film (A) / (B) / (A) / (C), and a co-extruded multilayer film having a thickness of 60 μm / 30 μm / 10 μm / 20 μm (total of 120 μm) was obtained.
（実施例６）
樹脂層（Ａ）用樹脂として、ＬＤＰＥ７０重量部とＬＬＤＰＥ３０重量部の混合樹脂を用い、樹脂層（Ｂ）用樹脂として、ＬＤＰＥ５０重量部、ＬＬＤＰＥ３０質量部及びＣＯＰ２０質量部の混合樹脂を用いた以外は実施例５と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ａ）／（Ｃ）＝６０μｍ／３０μｍ／１０μｍ／２０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Example 6)
A mixed resin of 70 parts by weight of LDPE and 30 parts by weight of LLDPE was used as the resin for the resin layer (A), and a mixed resin of 50 parts by weight of LDPE, 30 parts by weight of LLDPE and 20 parts by weight of COP was used as the resin for the resin layer (B). In the same manner as in Example 5, the thickness of each layer of the film was (A) / (B) / (A) / (C) = 60 μm / 30 μm / 10 μm / 20 μm (total 120 μm). A film was prepared to obtain a coextruded multilayer film.
（実施例７）
樹脂層（Ｂ）用樹脂として、ＬＬＤＰＥ９０質量部及びＣＯＰ１０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＬＤＰＥ７０質量部及びＰＢ−１ ３０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝１０μｍ／１０μｍ／１０μｍ（合計３０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。次いで、共押出多層フィルムの樹脂層（Ａ）の表面を、表面エネルギーが３６ｍＮ／ｍになるようにコロナ放電処理を施した。
(Example 7)
Implemented except that LLDPE 90 parts by mass and COP 10 parts by weight of mixed resin were used as the resin layer (B) resin, and LLDPE 70 parts by weight and PB-1 30 parts by weight of mixed resin were used as the resin layer (C) resin. In the same manner as in Example 1, a coextruded multilayer film was prepared so that the thickness of each layer of the film was (A) / (B) / (C) = 10 μm / 10 μm / 10 μm (total 30 μm). A multilayer film was obtained. Next, the surface of the resin layer (A) of the coextruded multilayer film was subjected to corona discharge treatment so that the surface energy was 36 mN / m.
上記で得られた共押出多層フィルムの樹脂層（Ａ）の表面に二軸延伸ポリエチレンテレフタレートフィルム（厚さ１２μｍ）をドライラミネーションで貼り合わせて、ラミネートフィルムを得た。この際、ドライラミネーション用接着剤としては、大日本インキ化学工業株式会社製の２液硬化型接着剤（ポリエステル系接着剤「ＬＸ６３Ｆ」及び硬化剤「ＫＰ９０」）を使用した。 A biaxially stretched polyethylene terephthalate film (thickness 12 μm) was bonded to the surface of the resin layer (A) of the coextruded multilayer film obtained above by dry lamination to obtain a laminate film. At this time, as a dry lamination adhesive, a two-component curable adhesive (polyester adhesive “LX63F” and a curing agent “KP90”) manufactured by Dainippon Ink & Chemicals, Inc. was used.
（比較例１）
樹脂層（Ｂ）用樹脂として、ＬＤＰＥ９２質量部及びＣＯＰ８質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＤＰＥ７０質量部及びＰＢ−１ ３０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）である共押出多層フィルムを得た。
(Comparative Example 1)
Implemented except that the resin for the resin layer (B) was a mixed resin of 92 parts by mass of LDPE and 8 parts by mass of COP, and the resin for the resin layer (C) was a mixed resin of 70 parts by mass of LDPE and 30 parts by mass of PB-1. In the same manner as in Example 1, a coextruded multilayer film in which the thickness of each layer of the film was (A) / (B) / (C) = 60 μm / 50 μm / 10 μm (total 120 μm) was obtained.
（比較例２）
樹脂層（Ｂ）用樹脂として、ＬＤＰＥ６０質量部及びＣＯＰ４０質量部の混合樹脂を用いた以外は比較例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）である共押出多層フィルムを得た。
(Comparative Example 2)
The thickness of each layer of the film is (A) / (B) / (C in the same manner as in Comparative Example 1 except that a mixed resin of LDPE 60 parts by mass and COP 40 parts by mass is used as the resin for the resin layer (B). ) = 60 μm / 50 μm / 10 μm (total 120 μm) was obtained.
（比較例３）
樹脂層（Ｃ）用樹脂として、ＬＤＰＥ６０質量部及びＰＢ−１ ４０質量部の混合樹脂を用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Comparative Example 3)
The thickness of each layer of the film is (A) / (B) in the same manner as in Example 1 except that a mixed resin of 60 parts by mass of LDPE and 40 parts by mass of PB-1 was used as the resin for the resin layer (C). / (C) = 60 μm / 50 μm / 10 μm (total of 120 μm) was prepared as a coextruded multilayer film to obtain a coextruded multilayer film.
（比較例４）
樹脂層（Ａ）用樹脂として、ＬＬＤＰＥを用い、樹脂層（Ｂ）用樹脂として、ＬＤＰＥ８０質量部及びＣＯＰ２０質量部の混合樹脂を用い、樹脂層（Ｃ）用樹脂として、ＬＤＰＥを用いた以外は実施例１と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝６０μｍ／５０μｍ／１０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Comparative Example 4)
Except that LLDPE was used as the resin for the resin layer (A), a mixed resin of 80 parts by mass of LDPE and 20 parts by mass of COP was used as the resin for the resin layer (B), and LDPE was used as the resin for the resin layer (C). In the same manner as in Example 1, a coextruded multilayer film was prepared so that the thickness of each layer of the film was (A) / (B) / (C) = 60 μm / 50 μm / 10 μm (total 120 μm). An extruded multilayer film was obtained.
（比較例５）
樹脂層（Ａ）用樹脂として、ＬＬＤＰＥを用い、樹脂層（Ｃ）用樹脂として、ＬＬＤＰＥを用いた以外は実施例５と同様の方法で、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ａ）／（Ｃ）＝４０μｍ／５０μｍ／２０μｍ／１０μｍ（合計１２０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。
(Comparative Example 5)
The thickness of each layer of the film was (A) / (B) in the same manner as in Example 5 except that LLDPE was used as the resin for the resin layer (A) and LLDPE was used as the resin for the resin layer (C). ) / (A) / (C) = 40 μm / 50 μm / 20 μm / 10 μm (total 120 μm) to produce a co-extruded multilayer film, thereby obtaining a co-extruded multilayer film.
（比較例６）
各樹脂層に用いる樹脂を比較例４で用いたものと同じものを用いて、フィルムの各層の厚さが（Ａ）／（Ｂ）／（Ｃ）＝１０μｍ／１０μｍ／１０μｍ（合計３０μｍ）となるように共押出多層フィルムを作製し、共押出多層フィルムを得た。次いで、共押出多層フィルムの樹脂層（Ａ）の表面を、表面エネルギーが３６ｍＮ／ｍになるようにコロナ放電処理を施した。
(Comparative Example 6)
Using the same resin as that used in Comparative Example 4 for each resin layer, the thickness of each layer of the film was (A) / (B) / (C) = 10 μm / 10 μm / 10 μm (total 30 μm). A coextruded multilayer film was prepared as described above to obtain a coextruded multilayer film. Next, the surface of the resin layer (A) of the coextruded multilayer film was subjected to corona discharge treatment so that the surface energy was 36 mN / m.
上記で得られた共押出多層フィルムの樹脂層（Ａ）の表面に二軸延伸ポリエチレンテレフタレートフィルム（厚さ１２μｍ）をドライラミネーションで貼り合わせて、ラミネートフィルムを得た。この際、ドライラミネーション用接着剤としては、大日本インキ化学工業株式会社製の２液硬化型接着剤（ポリエステル系接着剤「ＬＸ６３Ｆ」及び硬化剤「ＫＰ９０」）を使用した。 A biaxially stretched polyethylene terephthalate film (thickness 12 μm) was bonded to the surface of the resin layer (A) of the coextruded multilayer film obtained above by dry lamination to obtain a laminate film. At this time, as a dry lamination adhesive, a two-component curable adhesive (polyester adhesive “LX63F” and a curing agent “KP90”) manufactured by Dainippon Ink & Chemicals, Inc. was used.
上記の実施例１〜７及び比較例１〜６で得られた共押出多層フィルムを用いて、下記の試験及び評価を行った。 The following tests and evaluations were performed using the coextruded multilayer films obtained in Examples 1 to 7 and Comparative Examples 1 to 6.
（易カット性の評価）
上記で得られた共押出多層フィルムを、ＪＩＳ Ｋ７１２８に準拠して、それぞれ６３ｍｍ×７６ｍｍの大きさの試験片に切り出し、エルメンドルフ引裂試験機（テスター産業株式会社製）を用いて、引裂強さを測定した。なお、引裂強さは、共押出多層フィルムの成膜時の押出方向（縦（ＭＤ）方向）とこの方向と直交する方向（横（ＣＤ）方向）について測定した。得られた引裂強さから、下記の基準によって引き裂き性を評価した。
○：引裂強さが４５０未満である。
△：引裂強さが４５０以上、５５０未満である。
×：引裂強さが５５０以上である。
(Evaluation of easy cutability)
The coextruded multilayer film obtained above was cut into test pieces each having a size of 63 mm × 76 mm in accordance with JIS K7128, and the tear strength was measured using an Elmendorf tear tester (manufactured by Tester Sangyo Co., Ltd.). It was measured. The tear strength was measured in the extrusion direction (longitudinal (MD) direction) during film formation of the coextruded multilayer film and in the direction perpendicular to this direction (transverse (CD) direction). The tearability was evaluated from the obtained tear strength according to the following criteria.
○: Tear strength is less than 450.
Δ: Tear strength is 450 or more and less than 550.
X: Tear strength is 550 or more.
（直線カット性の評価）
上記で得られた共押出多層フィルムを、それぞれ１０ｃｍ×１０ｃｍの大きさの試験片に切り出し、そのフィルムの縦及び横の辺の中心位置に引き裂き用のノッチを入れ、一定の力と一定の速度で手で引き裂いた。試験片の引き裂き部分のずれから、下記の基準によって直線カット性を評価した。
○：引き裂き部分のずれが中心から１ｃｍ未満である。
△：引き裂き部分のずれが中心から１ｃｍ以上、２ｃｍ未満である。
×：引き裂き部分のずれが中心から２ｃｍ以上である。
(Evaluation of straight cut performance)
The co-extruded multilayer film obtained above is cut into test pieces each having a size of 10 cm × 10 cm, a notch for tearing is put in the center position of the vertical and horizontal sides of the film, a constant force and a constant speed. Torn by hand. From the deviation of the tearing part of the test piece, the linear cutability was evaluated according to the following criteria.
○: The deviation of the tearing portion is less than 1 cm from the center.
(Triangle | delta): The shift | offset | difference of the tearing part is 1 cm or more and less than 2 cm from the center.
X: The shift | offset | difference of the tearing part is 2 cm or more from the center.
（二次成形性の評価）
上記で得られた共押出多層フィルムを、それぞれ直径５ｃｍ、深さ３ｃｍの円柱状に真空成形による二次成形を行い、深絞りした成形品を得た。得られた成形品の成形状態及び底のコーナー部のピンホール状態を目視で観察し、下記の基準によって成形性を評価した。
○：外観が均一で、ピンホールがないもの。
×：外観が不均一か、あるいはピンホールの発生があるもの。
(Evaluation of secondary formability)
The co-extruded multilayer film obtained above was subjected to secondary forming by vacuum forming into a cylindrical shape having a diameter of 5 cm and a depth of 3 cm, respectively, to obtain a deep-drawn molded product. The molding state of the obtained molded product and the pinhole state of the bottom corner were visually observed, and the moldability was evaluated according to the following criteria.
○: Appearance is uniform and there is no pinhole.
X: Appearance is uneven or pinholes are generated.
（耐ピンホール性の評価）
上記で得られた共押出多層フィルムを、それぞれゲルボフレックステスター（テスター産業株式会社製）を用いて、常温で２００回屈曲させた後、屈曲部に発生したピンホールの数から、下記の基準によって耐ピンホール性を評価した。
○：ピンホールなし。
×：ピンホールあり。
(Evaluation of pinhole resistance)
Each of the coextruded multilayer films obtained above was bent 200 times at room temperature using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd.), and the following criteria were obtained from the number of pinholes generated in the bent portion. Was used to evaluate pinhole resistance.
○: No pinhole.
X: There is a pinhole.
（イージーピール性の評価）
上記で得られた共押出多層フィルム又はラミネートフィルムの樹脂層（Ｃ）の表面同士を重ね合わせ、ヒートシール温度１６０℃、シール圧力０．２ＭＰａ、シール時間１秒の条件でヒートシールを行った。次いで、ヒートシールしたフィルムを２３℃で自然冷却後、１５ｍｍ幅の短冊状に切り出して試験片とし、この試験片を２３℃、５０％ＲＨの恒温室において引張試験機（株式会社エー・アンド・ディー製）を用いて、３００ｍｍ／分の速度で９０°剥離を行い、ヒートシール強度を測定した。得られたヒートシール強度の値から、下記の基準によってイージーピール性を評価した。
○：ヒートシール強度が２〜１５Ｎ／１５ｍｍの範囲である。
×：ヒートシール強度が２〜１５Ｎ／１５ｍｍの範囲外である。
※表の方に、具体的にヒートシール強度の値を記載した方が良いと思います。
(Easy peel evaluation)
The surfaces of the resin layers (C) of the coextruded multilayer film or laminate film obtained above were overlapped, and heat sealing was performed under the conditions of a heat sealing temperature of 160 ° C., a sealing pressure of 0.2 MPa, and a sealing time of 1 second. Next, the heat-sealed film was naturally cooled at 23 ° C., and then cut into a 15 mm-wide strip to obtain a test piece. This test piece was subjected to a tensile tester (A & 90 ° peeling was performed at a rate of 300 mm / min, and the heat seal strength was measured. From the value of the obtained heat seal strength, the easy peel property was evaluated according to the following criteria.
○: Heat seal strength is in the range of 2 to 15 N / 15 mm.
X: Heat seal strength is outside the range of 2 to 15 N / 15 mm.
* I think that it is better to specify the heat seal strength value in the table.
上記で得られた結果を表１及び２に示す。 The results obtained above are shown in Tables 1 and 2.
表１の実施例１〜７の結果より、下記のことが分かった。 From the results of Examples 1 to 7 in Table 1, the following was found.
実施例１〜６の結果より、本発明の共押出多層フィルムは、フィルムの厚さが１２０μｍの厚膜であっても、縦方向のみならず横方向においても、少ない力で引き裂くことができ、かつイージーピール性も有し易開封性に優れていることが分かった。また、直線カット性に優れることから、安定した開封性も有する。さらに、深絞りの成形品を作製できる二次成形性を有し、耐ピンホール性にも優れていることが分かった。また、樹脂層（Ａ）〜（Ｃ）の各層に用いるＬＤＰＥ、ＬＬＤＰＥの含有比率を変化させることより、ＣＯＰの濃度を変えることなく引裂強さを制御できることが分かった。 From the results of Examples 1 to 6, the coextruded multilayer film of the present invention can be torn with a small force, not only in the vertical direction but also in the horizontal direction, even if the film thickness is 120 μm, It was also found that it has easy peel properties and is excellent in easy opening. Moreover, since it is excellent in linear cut property, it has the stable opening property. Furthermore, it has been found that it has secondary formability capable of producing a deep-drawn molded product and is excellent in pinhole resistance. It was also found that the tear strength can be controlled without changing the COP concentration by changing the content ratio of LDPE and LLDPE used in each of the resin layers (A) to (C).
実施例７の結果より、本発明の共押出多層フィルムは、ラミネートフィルム用のシーラントフィルムとして用いても、易カット性及び直線カット性、イージーピール性に優れることができることが分かった。 From the results of Example 7, it was found that the coextruded multilayer film of the present invention can be excellent in easy-cut property, straight-line cut property, and easy peel property even when used as a sealant film for a laminate film.
表２の比較例１〜６の結果より、下記のことが分かった。 From the results of Comparative Examples 1 to 6 in Table 2, the following was found.
比較例１の共押出多層フィルムは、樹脂層（Ｂ）中の環状オレフィン系樹脂（ＣＯＰ）の含有比率を１０質量％未満である８質量％とした例であるが、横方向の引き裂き性、縦方向及び横方向の直線カット性は不十分であることが分かった。 The coextruded multilayer film of Comparative Example 1 is an example in which the content ratio of the cyclic olefin resin (COP) in the resin layer (B) is 8% by mass, which is less than 10% by mass, It was found that the straight line cutability in the vertical direction and the horizontal direction was insufficient.
比較例２の共押出多層フィルムは、樹脂層（Ｂ）中の環状オレフィン系樹脂（ＣＯＰ）の含有比率が３０質量％を超える４０質量％とした例であるが、耐ピンホール性は不十分であることが分かった。 The coextruded multilayer film of Comparative Example 2 is an example in which the content ratio of the cyclic olefin resin (COP) in the resin layer (B) is 40% by mass exceeding 30% by mass, but the pinhole resistance is insufficient. It turns out that.
比較例３の共押出多層フィルムは、樹脂層（Ｃ）中のブテン−１系重合体（ＰＢ−１）含有比率が３０質量％を超える４０質量％とした例であるが、ヒートシール強度が小さ過ぎるため、実用的なヒートシールができないことが分かった。 The coextruded multilayer film of Comparative Example 3 is an example in which the content ratio of butene-1 polymer (PB-1) in the resin layer (C) is 40% by mass exceeding 30% by mass, but the heat seal strength is It was found that practical heat sealing was not possible because it was too small.
比較例４の共押出多層フィルムは、樹脂層（Ｃ）中にブテン−１系重合体（ＰＢ−１）を用いなかった例であるが、ヒートシール強度が高く、イージーピール性が不十分であることが分かった。 The coextruded multilayer film of Comparative Example 4 is an example in which the butene-1 polymer (PB-1) was not used in the resin layer (C), but the heat seal strength was high and the easy peel property was insufficient. I found out.
比較例５の共押出多層フィルムは、樹脂層（Ｃ）中にブテン−１系重合体（ＰＢ−１）を使用せず、４層構成の多層フィルムとした例であるが、ヒートシール強度が高く、イージーピール性が不十分であることが分かった。 The coextruded multilayer film of Comparative Example 5 is an example in which a butene-1 polymer (PB-1) is not used in the resin layer (C) and the multilayer film has a four-layer structure, but the heat seal strength is high. It was found to be high and easy peelability was insufficient.
比較例６の例は、比較例４と同様の共押出多層フィルムの厚さを３０μｍとし、ラミネートフィルム用のシーラントフィルムとして用いた例であるが、比較例４の共押出多層フィルムと同様に、ヒートシール強度が高く、イージーピール性が不十分であることが分かった。
The example of Comparative Example 6 is an example in which the thickness of the same co-extruded multilayer film as in Comparative Example 4 is 30 μm and is used as a sealant film for a laminate film. It was found that the heat seal strength was high and the easy peel property was insufficient.
Claims (6)
前記低密度ポリエチレン（ａ１）、（ｂ１）及び（ｃ１）の密度が０．９１５〜０．９３０ｇ／ｃｍ ３ であることを特徴とする二次成形用共押出多層フィルム。 Resin layer (A) comprising low density polyethylene (a1) and / or linear low density polyethylene (a2), and low density polyethylene (b1) and / or linear low density polyethylene (b2) 70 to 90% by mass And a resin layer (B) containing 10 to 30% by mass of a cyclic olefin resin (b3), 70 to 90% by weight of low density polyethylene (c1) and / or linear low density polyethylene (c2), and butene A resin layer (C) containing 10 to 30% by weight of a -1 polymer (c3), in the order of (A) / (B) / (C), or (A) / (B) / (A) The thickness of the film is 100 to 300 μm and the thickness of the resin layer (C) is 10 to 30 μm.
The low-density polyethylene (a1), (b1), and (c1) has a density of 0.915 to 0.930 g / cm 3 and is a co-extruded multilayer film for secondary molding .
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